Process for breaking petroleum emulsions



Patented Feb. 20, 1951 UNITED STATES PATENT OFFICE PROCESS FOR BREAKING PETROLEUM .EMULSIONS Melvin De Groote, St. Louis,'and Bernhard Keiser, Viebster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware N o-Drawing. Application Mayi5,i1950, Serial No. 160,378

.19 Claims. (Cl. 252340) our co-pending appfication, serial No. 64,469,

filedDecember 10,1948.

. Complementary -to theabove aspect of the invention is our companion invent-on concerned 'with the new chemical products or compounds used as the demulsifying agents in-said aforementioned processes or procedures, as well "as the application of such chemical compounds, products, and the-like, in various other arts and 'industriesalong with the method for manufac- "turng said new chemical products orcompounds "which-are of outstanding value in demulsiiication. See our co-pending application, Serial No. "64,457, filed DecemberlO, 1948.

Our invention provides an economical and "rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to ascut 'oil, roily oil, emulsifiedoil, etc, and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It-aTso-provides an economicaland rapid process for separating emulsions which have been prepared-under controled condit ons from mineral-oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification-and subsequent demuisification under the "conditions just mentioned areof significant value in removing impurities, particularly inorganic salts, from pipeline oil.

Demusification'as contemplated in the present appication includes the preventive step of commingling the demulsifier with the aqueous com 'ponent wh ch would or might subsequently become either phaseof the emulsion in the'absence ofsuc'h precautionary measure. Similarly, such demulsifier may-be mixed with the hydrocarbon component.

Briefly stated, the present process is concerned with the '"breaking-orresolving of petroleum emulsions by means of certain esters which are, in

turn, derivatives of specific synthetic products.

These products are, in turn, the oxyalkyla'tedderivatives of certain resins hereinafter specified.

Thus, the present invention is concerned with breaking petroleum emulsions of the water-ainoil type by subjecting the emulsion to the'action of a demuls fier including a mixed hydrophile ester in which the acylradicals include anacyl radical of "a'detergent-forming monocarboxy'acid having at least B-andnot over 32 carbon atoms in'conjunction with the acyl radical of an alpha halogen monocarboxy "acid having not over "6 carbon atoms, and in which the alcoholic radical is that of certain hydrophile polyhydric synthetic products; said .hydrophile synthetic products being oxyalkylation products of '(A) an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (B) an oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble phenolaldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atomsand reactive toward said phenol; said resin being formed in the substantial absence of trifunc- -tional phenols; said-phenol being of the formula in which R is a hydrocarbon radical havingrat least 4 and not more thanlZ carbon atoms and -s1ibstituted in the2,4,6 position; said oxyal-kylated res'inbeing characterized by the introduction'into themesin molecule of a plurality of divalent radi- "cals having the formula (R1O)n, in which R1 isa member selected from the class consisting "moles of alkylene oxide'be introduced for each phenolic nucleus; there being "presentgin the -ester, at least oneacyl radical of the alpha-halog n onocarboxyacid and at least "one acylradical of the detergent-forming monocarboxy acid, statistically taken, per resin molecule; and with the final proviso that the hydrophile properties of said ester, as well as said oxyalkylated resin in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

For purpose of convenience what i said hereinafter will be divided into four parts. Part 1 will be concerned with the production of the resin from a difunctional phenol and an aldehyde; Part 2 will be concerned with the oxyalkylation of the resin so as to convert it into a hydrophile hydroxylated derivative; Part 3 will be concerned with the conversion of the immediately aforementioned derivative into a total or partial ester by reaction with an acid, an ester, or other functional derivative, so as to obtain a compound of the kind previously specified and subsequently described in detail; and Part 4 will be concerned with the use of such esters as demulsifiers as hereinafter described.

PART 1 As to the preparation of the phenol-aldehyde resins reference is made to our co-pending ap- .plications, Serial Nos. 8,730 and 8,731, both filed February 16, 1948 (both now abandoned). In such co-pending applications we described a fusible, organic solvent-soluble, water-insoluble .resin polymer of the formula O H O H O H H H1 C C 011i);

In the instant application B may have as many as 12 carbon atoms,

as in the case of a resin obtained from a dodecylphenol. In the instant invention it may be first suitable to describe the alkylene oxides employed glycide, and methylglycide.

Any aldehyde capable of forming a methylol 'or a substituted methylol group and having not more than 8 carbon atoms is satisfactory, so long as it does not possess some other functional group or structure which will conflict with the resinification reaction or with the subsequent oxyalkyl- ;ation of the resin, but the use of formaldehyde, ..in its cheapest form of an aqueous solution, for the production of the resins i particularly advantageous.

Solid polymers of formaldehyde are more expensive and higheraldehydes are both less reactive, and are more expensive. Further- .more, the higher aldehydes may undergo other ,reactions which are not desirable, ..thus intro- 4 ducing difficulties into the resinification step. Thus acetaldehyde, for example, may undergo an aldol condensation, and it and most of the higher aldehydes enter into self-resinification when treated-with strong acids or alkalies. On the other hand, higher aldehydes frequently beneficially affect the solubility and fusibility of a resin. This is illustrated, for example, by the different characteristics of the resin prepared from para-tertiary amylphenol and formaldehyde on one hand, and a comparable product prepared fro-m the-same phenolic reactant and heptaldehyde on the other hand. The former, as shown in certain subsequent examples, is a hard, brittle, solid, whereas the latter is soft and tacky, and obviously easier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde. The employment of furfural requires careful control for the reason that in addi tion to its aldehydic function, furfural can form vinyl condensations by virtue of its unsaturated structure. The production of resins from furfural for use in preparing reactants for the present process is most conveniently conducted with weak alkaline catalysts and often with alkali metal carbonates. Useful aldehydes, in addition to formaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde, 2-ethylhexanal, ethylbutyraldehyde, heptaldehyde, and benzaldehyde, furfural and glyoxal. It would appear that the use of glyoxal should be avoided due to the fact that it is tetrafunctional. However, ourexperience has been that, in resin manufacture and particularly as described herein, apparently only one of the aldehydic functions enters into the resinification reaction. The inability of the other aldehydic function to enter into the reaction is presumably due to steric hindrance. Needless to say, one can use a mixture of two or more aldehydes although usually this has no advantage.

Resins of the kind which are used as intermediates in this invention are obtained with the use of acid catalysts or alkaline catalysts, or without the use of any catalyst at all. Among the useful alkaline catalysts are ammonia, amines, and quaternary ammonium bases. It is generally accepted that when ammonia and amines are employed as catalysts they enter into the condensation reaction and, in fact, may operate by initial combination with the aldehydic reactant. The compound hexamethylenetetramine illustrates such a combination. In light of these various reactions it becomes difiicult to present any formula which would depict the structure of the various resins prior to oxyalkylation. More will be said subsequently as to the diiference between the use of an alkaline catalyst and an acid catalyst; even in the use of an alkaline catalyst there is considerable evidence to indicate that the products are notidentical where different basic materials are employed. The basic materials employed include not only those previously enumerated but also the hydroxides of the alkali metals, hydroxides of the alkaline earth metals, salts of strong bases and weak acids such as sodium acetate, etc.

Suitable phenolic reactants include the following: Para-tertiarybutylphenol; para-secondarybutylphenol; para tertiary amylphenol; parasecondary amylphenol; para-tertiary-hexylphe- 1101; para isooctylphenol; ortho phenylphenol; para-phenylphenol; ortho benzylphenol; parabenzylphenol; and para cyclohexylphenol, and the corresponding ortho-para substituted metacresols and 3,5-xylenols. Similarly, one may use directly attached to'a condensed or fused polycyclic structure, are excluded. This matter, however, isclarified'bythe following consideration. 'lI'he phenols herein contemplated for reaction iim'ay'b'e indicated bythe following formula:

in which his :selected .fro-m the class consisting hydrogen atoms and hydrocarbon radicalsrhavaingatleaste carbon atoms .and notimore thanllZ azcafbonualtoms, .iwith .the proviso that one occurrence of R is the hydrocarbon substituent and the :other EilW-O occurrences are hydrogen atoms, Land "with the .iurtheriprovisio-n that one .or both mf thee and 5 positions bean'ethylsubstituted.

The above formula possibly can be restated "more conveniently in the ifollowing manner, to

Wit, that the phenol employed is of the following ""tornruiafwith the proviso that'R is-a hydrocarbon 'substitue'rit located in the 2,46 position, again withthe provision as' to 3 or 3,5 methyl substitution. This is conventional nomenclature, number-ing the various positions in the usual clockwise mahner, beginning with the hy'droxyl position as "one:

The .manufiactin'e of thermoplastic phenol-- t-aldehyde resins,;particularly from formaldehyde and adifunctionalrphenol, i. :e., aphencl :in which one of "the three reactive positions (2,4,6) lhas tbeen substituted by v a hydrocarbon group, and particularly byone having at least 4 carbon atoms nndmotmorethanlz 'oarbcn-atomszis well known. As has been previously pointed Elli, .rthereis no objection to .at.methyl radical .providedit .is present inithe .3 or 5 position.

Thermoplastic .or .fzusible'phenolaldehyde res- ".are usually .manufactured for the varnish *:trade and oil solubility is of prime importance. Forthis reason, the commonreactants employed wrehutylated phenols, .amylatedphenols, phenylphenols, etc. The methods employed in manufacturing such resins are similar to those employed in the manufacture of ordinary phenolformaldehyde resins, in that either an acid or alkaline catalyst is usually employed. The procedure usually differs from that employed in the manufacture of ordinary phenol-aldehyde resins in that phenol, being water-soluble, reacts readily with an aqueous aldehyde solution without further difiiculty, while when a water-insoluble phenol is employed some mod fication is usually adopted to increase the interfacial surface and thus cause reaction to take place. A common solvent is sometimes employed. Another procedure employs rather severe agitation to create a large interfacial area. Once the reaction starts to a moderate degree, it is possible that both reactants are somewhat soluble in the partially reacted mass and assist in hastening the reaction. We have found it desirable to employ a small proportion of an organic sulfo-acid as a catalyst, either alone or along with a mineral acid like .sulfuric or hydrochloric acid. For example, al kylated aromatic sulfonic acids are efiectively employed. Since commercial forms of such acids are commonly their alkali salts, it is sometimes convenient to use a small quantity of such :alkali salt plus a small quantity of strong mineral acid, as shown in the examples below. If desired,.such organic sulfo-acids may be prepared in situ in the phenol employed, by reacting concentrated sulfuric acid with a small proportion of the pheno1. .In .such cases where xylene is used as a solvent and concentrated sulfuric acid is employed, some sulfonation of the xylene probably occurs to produce the fsulfo-acid. Addition of 'a solvent such 'as xylene is advantageous as here- :in'after described in detail. Another variation of *procedure is to employsuch organc sulfo-acids, -in the'form of their salts, in connection with an alkali-catalyzed "resinification proced re. 'De- :tailed examples are .includedsubsequently.

Another advantage in the manufacture of the thermoplastic or fusible type of resin by the acid catalytic procedure is that, since a difunctional phenol is employed, an excess of an aldehyde, for

instance formaldehyde, may be employed 'without too'marked a change in conditions of reaction and ultmate product. There is usually little, if any, advantage, however, in using an excessover and above thestoichiometric proportions for the reason that such. excess may be lost and wasted. For all practical purposes the molar ratio of i..formaldehyde to phenol may be limited to 0.9 to

.12, with 1105 as the preferred ratio, or sufficient,

at least :theoretically,:to convert the remaining reactive :hydrogen atom of each terminal phenolic nucleus. Sometimes when higheraldehydes are used an excess of 'aldehydic reactant can be dis- "tilled ofi and thus recovered "from the reaction mass. This same procedure may be used with formaldehyde and excess-reactant recovered.

When .an alkaline catalyst is used the amount of aldehyde, particularly formaldehyde, may be increased overthe simple stoichiometric ratio of .cne-to-one;or thereabcuts. With the use of a1.-

.akine catalyst it has been recognized that considerably increased amounts of formaldehyde cmay bewused, :asizmuch as two moles of formal- :dehyde, for example, per mole of phenol, or even "more, with the result thatonly a small part of such aldehyde remains uncombined or .issubserquently liberated rduring cresinification. fitme- .tures which have been advanced to explain such .increased use of aldehydes are the following:

Such structures may lead to the production of cyclic polymers instead of linear polymers. For this reason, it has been previously pointed out that, although linear polymers have by far the most important significance, the present invention does not exclude resins of such cyclic structures.

Sometimes conventional resinification procedure is employed using either acid or alkaline catalysts to produce low-stage resins. Such resins may be employed as such, or may be altered or converted into high-stage resins, or in any event, into resins of higher molecular weight, by heating along with the employment of vacuum so as to split off water or formaldehyde, or both. Generally speaking, temperatures employed, particularly with vacuum, may be in the neighborhood of 175 to 250 C., or thereabouts.

It may be well to point out, however, that the amount of formaldehyde used may and does usually afiect the length of the resin chain. Increasing the amount of the aldehyde, such as formaldehyde, usually increases the size or -molecular Weight of the polymer.

In the hereto appended claims there is specified, among other things, the resin polymer containing at least 3 phenolic nuclei. Such mini.. mum molecular size is most conveniently determined as a rule by cryoscopic method using benzene, or some other suitable solvent, for instance, one of those mentioned elsewhere herein as a solvent for such resins. As a matter of fact, using the procedures herein described or any conventional resinification procedure will yield products usually having definitely in excess of 3 nuclei. age of 4, 5 or 5 nuclei per unit is apt to be formed as a minimum in resinification, except under certain special conditions where dimerization may occur.

However, if resins are prepared at substantially higher temperatures, substituting cymene, tetralin, etc., or some other suitable solvent which boils or refluxes at a higher temperature, instead of xylene, in subsequent examples, and if one doubles or triples the amount of catalyst, doubles or triples the time of refluxing, uses a marked exc ss In other words, a resin having an averaccordance with the invention, those derived of formaldehyde or other aldehyde, then the In the appended claims we have used from low-stage resins, as just defined, will contain at least one acyl radical of an-alpha-halogen monocarboxy acid having not over 6 carbon atoms and one acyl radical of a detergent-f0rm ing monocarboxy acid for each 7 phenolic nuclei. In higher stage resins the ratio may be smaller. However, it is advantageous, even with higher stage resins to introduce at least one acyl radical of each type of acid for every 7 phenolic nuclei. This does not mean, of course, that each resin molecule has one acyl radical of each type linked to it, as the requirements as to the presenceof the acyl radicals are statistically taken.

The molecular weight determinations, of course, require that the product be completely soluble in the particularsolvent selected as, for instance, benzene. The molecular weight determination of such solution may involve either the freezing point as in the cryoscopic method, 'or, less conveniently perhaps, the boiling point in an ebullioscopic method. The advantage of the ebullioscopic method is that, in comparison with the cryoscopic method, it is more apt to insure complete solubility. One such common method to employ is that of Menzies and Wright (see J. Am. Chem. Soc. 43, 2309 and 2314 (1921)). Any suitable method for determining molecular weights will serve, although almost any procedure adopted has inherent limitations. A good met od for determining the molecular weights of resins, especially solvent-soluble resins, is the cryoscopic procedure of Krumbhaar which employs diphenylamine as a solvent (see Coating and Ink Resins, page 157, Reinhold Publishing Co., 1947). Y

Subsequent examples will illustrate the use of an acid catalyst, an alkaline catalyst, and no catalyst. As far as resin manufacture per se is concerned, we prefer to use an acid catalvst, and particularly a mixture of an organic sulfo-acid and a mineral acid, along with a suitable solvent, such as xylene, as hereinafwr illustrated in detail. However, we have obtained products from resins obtained by use of an alkaline catalyst which were just as satisfactory as those obtained employing acid catalysts. Sometimes a combination of both types of catalysts is usedin difierent stages of resinification. Resins so obtained are also perfectly satisfactory.

In numerous instances the higher molecular weight resins, i. e., those referred to as highstage resins, are conveniently obtained by subjecting lower molecular weight resins to vacuum distillation and heating. Although such procedure sometimes removes only a modest amount or even perhaps no low polymer, yet it is almost certain to produce further polymerization. For instance, acid catalyzed resins'obtained in the usual manner and having a molecular weight indicating the presence of approximately 4 phenolic units or thereabouts may be subjected to such treatment, with the result that one obtains a resin having approximately double this molecular weight. The usual procedure is to use a secondary step, heating the resin in the presence or absence of an inert gas, including steam, or by use of vacuum.

We have found that under the usual conditions of resinification employing phenols of the kind here described, there is little or no tendency to form binuclear compounds, i. e'., dimers, resulting from the combination, for example, of 2 moles of a phenol and one mole of formaldehyde, particularly. where the substituent has, 4 or 5 carbon 9, atoms; Where the number or carbon atoms in a substituent approximates the upper limit speci' fied herein, there may be some tendency to dimerization, The usual procedure to obtain a. dimer involves an enormously large excess of the phenol, for instance, 8 to 10 moles per mole of aldehyde. Substituted dihydroxydiphenylmethanes obtained from substituted phenols are not resins as that term is used herein.

Although any conventional procedure. ordinarily employed may be used in the manufacture of the herein contemplated resins or, for that matter, such resins may be purchased in the open market, we have found it particularly desirable to use the procedures described elsewhere: herein, and. employing a combination or an organic suifoacid and a. mineral. acid as a. catalyst, and xylene; as a solvent. By way of illustration, certain subsequent examples are included, but it is to. be understood the herein described invention isnot concerned with the resins per se or with any par-- ticular method of manufacture but. is concerned with the use of reactants obtained by the subsequent oxyalkylation thereof. The phenol-aldehyde resins may be prepared in any suitable manner.

Oxyalkylation, particularly oxyethylation which is the preferred reaction, depends on contact. between a non-gaseous phase and a gaseous phase. It can, for example, be carried out by melting the thermoplastic resin and subjecting it to treatment with ethylene oxide or the like, or by treating a suitable solution or suspension. Since the melting points of the resins are often higher than desired in the initial stage of oxyethylation, we have found it advantageous to use a solution or suspension of thermoplastic resin in an inert solvent such as xylene. Under such circumstances, the resin obtained in the usual manner is dissolved by heating in xylene under a reflux condenser or in any other suitable manner. Since xylene or an equivalent inert solvent is present or may be present during oxyalkylation, it is obvious there is no objection to having a solvent present during the resiniiying stage if, in addition to being inert towards the resin, it is also inert towards the reactants and also inert towards water. Numerous solvents, particularly of aromatic or cyclic nature, are suitably adapted for such use. Examples of such solvents are xylene, cymene, ethyl benzene, propyl benzene, mesitylene, decalin (decahydronaphthalene), tetralin ('tetrahydronaphthalene), ethylene glycol diethylether, diethylene glycol diethylether,

and tetraethylene glycol dimethylether, or mix tures of one or more. Solvents such as dichloroethylether, or dichloropropylether may be employed either alone or in mixture but have the objection that the chlorine atom in the compound may slowly combine with the alkaline catalyst employed in oxyethylation. Suitable solvents may be selected from this group for molecular weight determinations.

The use of such solvents is a convenient expedient in the manufacture of the thermoplastic resins, particularly since the solvent gives a more liquid reaction mass and thus prevents overheating, and also because the solvent can be employed in connection with a reflux condenser and a, water trap to assist in the removal of water of reaction and also water present as part of the formaldehyde reactant when an aqueous solution of formaldehyde is used. Such aqueous solution, of course, with the ordinary product of commerce containing about 37%.;% to 40% formaldehyde,

10' is the preferred reactant. When such. solvent is used it. is advantageously added at the beginning of the resinification procedure Or before the reaction has proceeded. very far.

The solvent can be removed afterwards by distillation with or without the use of vacuum, and a final higher temperature can be employed. to; complete reaction if desired. In many instances it is most desirable to permit part of the solvent, particularly when it is inexpensive, e. g., xylene, to remain behind in a predetermined amount so as to have a resin which can be handled more conveniently in the oxyalkylation stage. If a more expensive solvent, such as decalin, is employed, xylene or other inexpensive solvent may be added after the removal. of decalin, if desired.

In preparing resins from difunctional phenols it: is common to employ reactants of technical grade. The. substituted phenols herein contemplated are usually derived from hydroxybenzene. As a. rule, such substituted phenols are comparatively free from unsubstituted phenol. We have generally found that the amount present is considerably less than 1% and not infrequently in. the neighborhood of T16 of 1%, Or even less- The amount of the usual trifunctional phenol, such as hydroxybenzene or metacresol, which can be. tolerated is determined by the fact that actual cross-linking, if it takes place even infrequently, must not be suflicient to cause insolubility at the completion of the resinification stage or the lack of hydrophile properties atthe completion of the oxyalkylation stage.

The exclusion of such trifunctional phenols as h-ydroxybenzene or metaoresol is not based on the fact that the mere random or occasional inclusion of an unsubstituted phenyl nucleus in the resin molecule or in one of several molecules, for example, markedly alters the characteristics of the oxyalkylated derivative. The presence of a phenyl radical having a reactive hydrogen atom available or having a hydroxymethylol or a substituted hydroxymethylol group present is a potential source of cross-linking either during resini-fication or oxyalkylation. Cross-linking leadseither to insoluble resins or to non-hydrophiIic products resulting from the o-xyalhylation proce dure. With this rationale understood, it is obvious that trifunctional phenols are tolerable only in a minor proportion and should not be present to the extent that insolubi-li-ty is produced inthe resins, or that the product resulting from oxyalkylation is gelatinous, rubbery, or at least not hydrophile. As to the rationale of resinification, note particularly what is said hereafter in differ entiating between resoles, Novolaks, and resins obtained solely from diiunctional phenols.

Previous reference has been made to the fact that fusible organic solvent-soluble resins are usually linear butmay be cyclic. Such more complicated structure may be formed, particularly if a resin prepared in the usual manner is converted into a, higher stage resin by heat treatmentiitr vacuum as previously mentioned. This again is a reason for avoiding any opportunity for crosslinking due to the presence of any appreciable amount of trifunctional phenol. In other words, the presence of such reactant may cause crosslinking in aconventional re'sinification procedure, or in the oxyalkylationprocedure, or in the heat and vacuum treatment if it is employed aspart of resin manufacture.

Our routine procedure in examining a. phenol for suitability for preparing intermediates to. be usedin practicing the invention is to preparea resin employing formaldehyde in excess (1.2 moles of formaldehyde per mole of phenol) and using an acid catalyst in the manner described in Example la of our patent 2,499,370 granted March 7,1950. Ifthe resin so obtained is solvent-soluble in any one of the aromatic or other solvents previously referred to, it is then subjected to oxyethylation. During oxyethylation a temperature is-employed of approximately 150 to 165 C. with addition of at least 2 and advantageously up to 5 moles of ethylene oxide per phenolic hydroxyl. The oxyethylation is advantageously conducted so as to require from a few minutes up to 5 to hours. If the product so obtained is solvent-soluble and self-dispersing or emulsifiable, or has emulsifying properties, the phenol is perfectly satisfactory from the standpoint of trifunctional phenol content. The solvent may be removed prior to the dispersibility or emulsifiability test. When a product becomes rubbery during oxyalkylation due to the presence of a small amount of trireactive phenol, as previously mentioned, or for some other reason, it may become extremely insoluble, and no longer qualifies as being hydrophile as herein specified. Increasing the size of the aldehydic nucleus, for instance using heptaldehyde instead of formaldehyde, increases tolerance for trifunctional phenol.

The presence of a trifunctional or tetrafunctional phenol (such as resorcinol or bisphenol A) isapt to produce detectable cross-linking and insolubilization but will not necessarily do so, especially if the proportion is small. Resinification involving difunctional phenols only may also produce insolubilization, although this seems to be an anomaly or a contradiction of what is sometimes said in regard to resinification reactions involving difunctional phenols only. This is presum ably due to cross-linking. This appears to be contradictory to what one might expect in light of the theory of functionality in resinification. It is true that under ordinary circumstances, or rather under the circumstances of conventional resin manufacture, the procedures employing difunctional phenols are very apt to, and almost invariably do, yield solvent-soluble, fusible resins. However, when conventional procedures are employed in connection with resins for varnish manufacture or the like, there is involved the matter of color, solubility in oil, etc. When resins of the same type are manufactured for the herein contemplated purpose, i. e., as a raw material to be subjected to oxyalkylation, such criteria of selection are no longer pertinent. Stated another way, one may use more drastic conditions of resinification than those ordinarily employed to produce resins for the present purposes. Such more drastic conditions of resinification may include increased amounts of catalyst, higher temperatures, longer tim of reaction, subsequent reaction involving heat alone or in combination with vacuum, etc. Therefore, one is not only concerned with the resinification reactions which yield the bulk of ordinary resins from difunctional phenols but also and particularly with the minor reactions of ordinary resin manufacture which are of importance in the present invention for the reason that they occur under more drastic conditions of resinification which may be employed advantageously at times, and they may lead to crosslinking.

In this connection it may. be well to point out that part of these reactions are now understood or explainable to a greater or lesser degree in light of a. most recent investigation. Reference is made to the researches of Zinke and his coworkers, Hultzsch and his associates, and to' von Eulen and his co-workers, and others. As to a' bibliography of such investigations, see Carswell,

Phenoplasts, chapter 2. These investigators limited much of their work to reactions involving phenols having two or less reactive hydrogen atoms. Much of what appears in these most recent and most up-to-date investigations is pertinent to the present invention insofar that much of it is referring to resinification involving difunctional phenols.

nnnnnnnnnnnnn For the moment, it may be simpler to consider a most typical type of fusible resin and forget for the time that such resin, at least under certain circumstances, is susceptible to further compli- 1 cations. Subsequently in the text it will be pointed out that cross-linking or reaction with excess formaldehyde may take place even with one of such most typical type resins. This point is made for the reason that insolubles must be avoided in order to obtain the products herein contemplated for use as reactants.

The typical type of fusible resin obtained from a para-blocked or ortho-blocked phenol is clearly differentiated from theNovolak type or resole type of resin. Unlike the resole type, such typical type para-blocked or ortho-blocked phenol resin may be heated indefinitely without passing into an infusible stage, and in this respect is similar to a Novolak. Unlike the Novolak type the addition of a further reactant, for instance, more aldehyde, does not ordinarily alter fusibility of the difunctional phenol-aldehyde type resin; but such addition to a Novolak causes cross-linking by virtue of the available third functional position.

What has been said immediately preceding is,

mation of insolubles during resin manufacture or, the subsequent stage of resin manufacture where heat alone, or heat and vacuum, are employed, or in the oxyalkylation procedure. In its simplest presentation the rationale of resinification involving formaldehyde, for example, and a difunctional phenol would not be expected to form cross-links. However, cross-linking sometimes occurs and it may reach the objectionable stage. However, provided that the preparation of resins simply takes into cognizance the present knowledge of the subject, and employing preliminary, exploratory routine examinations as herein indicated, there is not the slightest difficulty in preparing a very large number of resins of various types and from various reactants, and by means of different catalysts by different procedures, all of which are eminently suitable for the herein. described purpose. Now returning tothe thought that cross-linking: can take place, even when difunctional phenols are used exclusively, attention is directed to'the following: Somewhere during the course of resin manufacture therev may be a potential cross-linking combination formed but actual cross-linking may not take place until the sub sequent stage is reached, i. e., heat and vacuum stage, or oxyalkylation stage. This situation may be related or explained in terms of a theory of flaws, or Lockerstellen, which is employed in explaining flaw-forming groups due to the fact that .a. CI-IzOI-I radical and H atom may not lie in the same plane in the manufacture of. ordinary phenol-aldehyde resins.

Secondly, the formation or absence of formation of insolubles may be related to the aldehyde used and the ratio of aldehyde, particularly formaldehyde, insofar that a slight variation may, under circumstances not understandable, produce insolubillzation. The formation, of the insoluble resin is apparently very sensitive, to the quantity of formaldehyde employed and a. slight increase in the proportion of formaldehyde may lead to the formation of insoluble gel lumps. The cause of insoluble resin formation is not clear, and nothing is known as to the, structure of, these resins.

All that has been said previously herein as regards resinification has avoided the specific reference. to activity of a methylene hydrogen atom. Actually there is a possibility that under some drastic conditions cross-linking may take place through formaldehyde addition to the methylene bridge, or some other reaction involving a methylone hyd ogen atom.

Finally, there is some evidence. that, although the meta positions are not ordinarily reactive,

possibly at times methylol groups or the like are formed at the meta positions; and if this were the case it may be a suitable explanation of abnormal cross-linking.

Reactivity of a resin towards excess aldehyde, for instance formaldehyde, is not to be taken as a criterion of rejection for use as a reactant. In other words, a phenol-aldehyde resin which is thermoplastic and solvent-soluble, particularly if xylene-soluble, is perfectly satisfactory even.

though retreatment with more aldehyde may change its characteristics markedly in regard to both fusibility and solubility. Stated another way, as far as resins obtained from difunctional phenols are concerned, they may be either formaldehyde-resistant or not formaldehyde-res'istant.

Referring again to the resins herein, contemplated as reactants, it is to be noted that they are themoplastic phenol-aldehyde resins derived from difunctional phenols and are clearly distinguished from Novolaks or resoles. When these resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is often a comparatively soft or pitchlike resin at ordinary temperature. Such resins become comparatively fluid at 110 to 165 C. as a rule and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

Reference has been made to the use of the word fusible. Ordinarily a thermoplastic resin is identified as one which can be heated repeatedly and still not lose its thermoplasticity. It is recognized, however, that one may have a resin which is initially thermoplastic but on repeated heating may become insoluble in an organic solvent, or at least no longer thermoplastic, due to the fact that certain changes take place very slowly. As far asthe present invention is concerned, it is obvious that a resin to be suitablev need only be suificiently fusible to permit proc-. essing to produce our oxyalkylated products and not yield insolubles or cause insolubilization or gel formation, or rubberiness, as previously described. Thus resins which are, strictly speaking. fusible but not necessarily thermoplastic in the most rigid sense that such terminology would be applied to the mechanical properties of a resin, are useful intermediates. The bulk of all fusible resins of the kind herein described are thermoplastic.

The fusible or thermoplastic resins, or solventsoluble resins, herein employed as reactants, are water-insoluble, or have no appreciable hydro phile properties. The hydrophile property is introduced by oxyalkylation. In the hereto appended claims and elsewhere the expression water-insoluble is used to point out this characteristic of the resins used.

In the manufacture of compounds herein employed, particularly for demulsification, it is obvious that the resins can be obtained by one of a number of procedures. In the first place, suitable resins are marketed by a number of companies and can be purchased in the open market; in the second place, there are a wealth of examples of suitable resins described in the literature. The third procedure is to follow the directions of the present application.

The polyhydric reactants, i. e., the oxyalkylation-susceptible, water-insoluble, organic solventsoluble, fusible, phenol-aldehyde resins derived from difunctional phenols, used as intermediates to produce the products used in accordance with the invention, are exemplified by Examples Nos. la through 103a of our Patent 2,499,370, granted March '7, 1950, and reference is made to that patent for examples of the oxyalkylated resins used as intermediates.

Previous reference has been made to the use of a single phenol as herein specified, or a single reactive aldehyde, or a single oxyalkylating agent. Obviously, mixtures of reactants may be employed, as for example a mixture of parabutylphenol and para-amylphenol, or a mixture of para-butylphenol and para-hexylphenol, or para-butylphenol and para-phenylphenol. It is extremely difficult to depict the structure of a resin derived from a single phenol. When mixtures of phenols are used, even in equimolar proportions, the structure of the resin is even more indeterminable. In other words, a mixture involving para-butylphenol and para-amylphenol might have an alternation of the two nuclei or one might have a series of butylated nuclei and then a series or amylated nuclei. If a mixture of aldehydes is employed, for instance, acetaldehyde and butyraldehyde, or acetaldehyde and formaldehyde, or bsnzaldehyde and acetaldehyde, the final structure of the resin becomes even more complicated and possibly depends on the relative reactivity of the aldehydes. For that matter, one might be producing simultaneously two different resins, in what would actually be a mechanical mixture, although such mixture might exhibit some unique properties as compared with a mixture of the same two resins prepared separately. Similarly, as has been suggested, one might use a combination of oxyalkylating agents; for instance, one might partially oxyalkylate with ethylene oxide and then finish off with propylene oxide. It is understood that the oxyalkylated derivatives of such resins, derived from such plurality of reactants, instead 15 of being limited to a single reactantfroni each of the three classes, is contemplated and here included for the reason that they are obvious variants.

PART 2 Having obtained a suitable resin of the kind described, such resin is subjected to treatment with a low molal reactive alpha-beta olefin oxide so as to render the product distinctly hydrophile in nature as indicated by the fact that it becomes seli-emulsifiable or miscible or soluble in water, or self-dispersible, or has emulsifying properties. The olefin oxides employed are characterized by the fact that they contain not over 4 carbon atoms and are selected from the class consisting of ethylene oxide, propylene oxide,-

butylene oxide, glycide, and methylglycide.

Glycide may be, of course, considered as a hydroxy propylene oxide and methyl glycide as a hydroxy butylene oxide. In any event, however, all such reactants contain the reactive ethylene oxide ring and may be best considered as derivatives of or substituted ethylene oxides. ubilizing effect of the oxide is directly proportional to the percentage of oxygen present, or specifically, to the oxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is 2:3; and in methyl glycide, 1:2. In such compounds, the ratio is very favorable to the production of hydrophile or surfaceactive properties. However, the ratio, in propylene oxide, is 1 :3, and in butylene oxide, lz i. Obviously, such latter two reactants are satisfactorily employed only where the resin composition is such as to make incorporation of the desired property practical. In other cases, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. They are usable in'conjunction with the three more favorable alkylene oxides in all cases. For instance, after one or several propylene oxide or butylene oxide molecules have been attached to the resin molecule, oxyalkylation may be satisfactorily continued using the more favorable members of the class, to produce the desired hydrophile product. Used alone, these two reagents may in some cases fail to produce sufiiiciently hydrophile derivatives because of their relatively low oxygen-carbon ratios.

Thus, ethylene oxide is much more effective than propylene oxide, and propylene oxide .is more efiective than butylene oxide. Hydroxy propylene oxide (glycide) is more eiiective than propylene oxide. Similarly, hydroxy butylene oxide (methyl glycide) is more effective than butylene oxide. alkylene oxide available and is reactive, its use is definitely advantageous, and especially in light of its high oxygen content. Propylene oxide is less reactive than ethylene oxide, and butylene oxide is definitely less reactive than propylene oxide. On the other hand, glycide may react with almost explosive violence and must be handled with extreme care.

The oxyalkylation of resins of the kind from which the initial reactants used in the practice of the present invention are prepared is advantageously catalyzed by the presence of an alkali. Useful alkaline catalysts include soaps, sodium acetate, sodium hydroxide, sodium methylate, caustic potash, etc. The amount of alkaline catalyst usually is between 0.2% to 2%. The tem- The 501- Since ethylene oxide is the cheapest.

amama perature employed may vary from rdom temperature to as'high as 200 C. The reaction may beconducted with or without pressure, i. e., f10m stantially the same procedure as used for oxyalkylation of other organic materials having reactive phenolic groups.

It may be necessary to allow for the acidity of a resin in determining the amount of alkaline catalyst to be added in oxyalkylation. For instance, if a nonvolatile strong acid such as sulfuric acid is used to catalyze the resinification reaction, presumably after being converted into a sulfonic acid, it may be necessaryand is usually advantageous to add an amount of alkali equal stoichiometrically to such acidity, and include added alkali over and above this amount i as the alkaline catalyst. It is advantageous to conduct the oxyethylaej tion inpresenee of an inert solvent such as xylene,

cymene, decalin, ethylene glycol diethylether, di-f ethyleneglycol diethylether, or the like, although with many resins, the oxyalkylation proceeds satisfactorily without a solvent. Since xylene is cheap and may be permitted to be present in the; final product used as a demulsifier, it is our pref- This is particularly true in the manufacture of products from low-stage erence to use xylene.

resins, i. e., of 3 and up to and including '7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated, the pressure readings of course represent total pressure, that is, the com-.., bined pressure due to xylene and also due to resins, a solvent such as xylene can be eliminated in either one of two ways: After the introduc tion of approximately 2 or 3 moles of ethylene oxide, for example, per phenolic nucleus, there is a definite drop in the hardness and melting point of the resin. At this stage, if xylene or a.

similar solvent. has been added, it can be eliminated by distillation (vacuum distillation if desired) and the subsequent intermediate, being comparatively soft and solvent-free, can be re-, acted further in the usual manner with ethylene oxide or some other suitable reactant.

Another procedure is to continue the reaction.

to completion with such solvent present and then eliminate the solvent by distillation in the cus-.

tomary manner.

Another suitable procedure is to use propylene oxide or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the pow-- oxide is more reactive than propylene oxide orbutylene oxide, the final product may containsome unreacted propylene oxide or butylene 0x After a solution has been obtained which- 17' ide which can be eliminated by volatilization or distillation in any suitable manner.

Attention is directed to the fact that the resins herein described must be fusible or soluble in an organic solvent. Fusible resins invariably are soluble in one or more organic solvents such as those mentioned elsewhere herein. It is to be emphasized, however, that the organic solvent employed to indicate or assure that the resin meets this requirement need not be the one used in oxyalkylation. Indeed, solvents which are susceptible to oxyalkylation are included in this group of organic solvents. Examples of such solvents are alcohols and alcohol-ethers. However, where a resin is soluble in an organic solvent, there are usually available other organic solvents which are not susceptible to oxyalkylation, useful for the oxyalkylation step. In any event, the organic solvent-soluble resin can be finely powdered, for instance to 100 to 200 mesh, and a slurry or suspension prepared in xylene or the like, and subjected to oxyalkylation. The fact that the resin is soluble in an organic solvent or the fact that it is fusible means that it consists of separate molecules. Phenol-aldehyde resins of the type herein specified possess reactive hydroxyl groups and are oxyalkylation susceptible.

Considerable of what is said immediately hereinafter is concerned with ability to vary the hydrophile properties of the hydroxylated intermediate reactants from minimum hydrophile properties to maximum hydrophile properties. Such properties in turn, of course, are effected subsequently by the acids employed for esterification and the quantitative nature of the esterificaiton itself, i. e., whether it is total or partial. It may be well, however, to point out what has been said elsewhere in regard to the hydroxylated intermediate reactants. See, for example, our co-pending applications, Serial Nos. 8,730 and 8,731, both filed February 16, 1948, and Serial No. 42,133, filed August 2, 1948, and Serial No. 42,134, filed August 2, 1948 (all four cases now abandoned). The reason is that the esterification, depending on the acids selected, may vary the hydrophile-hydrophobe balance in one direction or the other, and also invariably causes the development of some property which makes it inherently different from the reactants from which the derivative ester as obtained.

Referring to the hydrophile hydroxylated intermediates, even more remarkable and equally difiicult to explain, are the versatility and the utility of these compounds considered as chemical reactants as one goes from minimum hydrophile property to ultimate maximum hydrophile property. For instance, minimum hydrophile property may be described roughly as the point where two ethylenecxy radicals or moderately in excess'thereof are introduced per phenolic hydroxyl. Such minimum hydrophile property or sub-surface-activity or minimum surface-activity .means that the product shows at least emulsifying properties or self-dispersion in cold or even in warm distilled water to 40 C.) in concentrations of 0.5% to 5.0%. These materials are generally more soluble in cold water than warm water, and may even be very insoluble in boiling water. Moderately high temperatures aid in reducing the viscosity of the solute under examination. Sometimes if one continues to shake a hot solution, even though cloudy or containing an insoluble phase, one finds that solution takes place to give a homogeneous phase as the mixture cools. Such self-dispersion tests are conducted in the absence of an insoluble solvent.

When the hydrophile-hydrophobe balance is above the indicated minimum (2 moles of ethylene oxide per phenolic nucleus or the equivalent) but insuiiicient to give a sol as described immediately preceding, then, and in that event hydrophile properties are indicated by the fact that one can produce an emulsion by having present 10% to 50% of an inert solvent such as xylene. All that one need to do is to have a xylene solution within the range of 50 to parts by weight of oxyalkylated derivatives and 50 to 10 parts by weight of xylene and mix such solution with one, two or three times its volume of distilled water and shake vigorously so as to obtain an emulsion which may be of the oil-in-water type or the water-in-oil type (usually the former) but,

in any event, is due to the hydrophile-hydrophobe balance of the oxyalkylated derivative. We prefer simply to use the xylene diluted derivatives, which are described elsewhere, for this test rather than evaporate the solvent and employ any more elaborate tests, if the solubility is not sufiicient to permit the simple sol test in water previously noted.

If the product is not readily water soluble it may be dissolved in ethyl or methyl alcohol, ethylene glycol diethylether, or diethylene glycol diethylether, with a little acetone added if required, making a rather concentrated solution, for instance 40% to 50%, and then adding enough of the concentrated alcoholic or equivalent solution to give the previously suggested 05% to 5.0% strength solution. If the product is self-dispersing (i. e., if the oxyalkylated product is a liquid or a liquid solution self-emulsifiable) such sol or dispersion is referred to as at least semi-stable in the sense that sols, emulsions, or dispersions prepared are relatively stable, if they remain at least for some period of time, for instance 30 minutes to two hours, before showing any marked separation. Such tests are conducted at room temperature (22 C.) Needless to say, a test can be made in presence of an insoluble solvent such as 5% to 15% of xylene, as noted in previous examples. If such mixture, i. e., containing a water-insoluble solvent, is at least semi-stable, obviously the solvent-free product would be even more so. Surface-activity representing an advanced hydrophile-hydrophobe balance can also be determined by the use of conventional measurements hereinafter described. One outstanding characteristic property indicating surfaceactivity in a material is the ability to form a permanent foam in dilute aqueous solution, for example, less than 0.5%, when in the higher oxyalkylated stage, and to form an emulsion in the lower and intermediate stages of oxyalkylation.

Allowance must be made for the presence of a solvent in the final product in relation to the hydrophile properties of the final product. The principle involved in the manufacture of the herein contemplated compounds for use as polyhydric reactants is based on the conversion of a hydrophobe or non-hydrophile compound or,

mixture of compounds into products which are distinctly hydrophile, at least to the extent that they have emulsifying properties or are selfemulsifying; that is, when shaken with water they produce stable or semi-stable suspensions, or, in the presence of a water-insoluble solvent, such as xylene, an emulsion. In demulsification, it is sometimes preferable to use a product having markedly enhanced hydrophile properties aware over and above'the "initial stage of self emulsifi ability,- although we have found that with prod nets of the type used herein, most efficacious results are obtained with products whichdo not have hydrophile properties-beyond the stage of self-dispersibility.

More highly oxyalkylated resins give colloidal solutions or sols which show typical properties comparable to ordinary surface-active agents. Such conventional surface-activity may be measured by determining the surface tension and the interfacial tension against'paraflin oil or the like. At the initial and lower stages of oxyalkylation, surface-activity is not suitably determined in this same manner but one may employ an emulsification test. Emulsions come into existence as a rule through the presence of-a surface-active emulsifying agent. Some surface-active emulsifying agents such as mahogany soap may produce a water-in-oil emulsion or an oilin-water emulsion'depending upon the-ratio of the two phases, degree of agitation, concentration of emulsifying agent, etc.

The sameis true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing-a xylene-Water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufiicient to reduce; even a tacky resinous product to a solution which -'is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-inwater type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly-in the lowest stage of oxyalkylation, one may obtain a waterin xylene emulsion (water-'in-oil type) which is apt to reverse on more vigorous shaking and further dilution with water. i 11 If in-doubt' as to this propertyfcompar-ison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst andth'en followed by-oxyalkylation using 2 moles ofeth' ylene oxide'for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has amolecular weight indicating about 4 /2 units *per resin molecule. Such resin, when diluted with an equal weight of Xylene, will serve to illustrate-the above emulsification test.

In a few instances, the resin may not be'suf' :ficiently solublein xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood" that such mixture, or any-other similar'mixture, is considered the equivalent'of xylene for thepurpose of this test.

In many cases, there is no doubt as to'the presonce or absence of hydrophile or surface-active fact that a reagent is capable of producing-a dis-;

persion in water is proof that it is distinctly hydrophile.

In doubtful cases,- comparison can re 'made with the butylphenol foi maldehyde 'iesiii analog wherein 2 moles of ethylene oxide have been introducedfor each phenolic nucleus.

The presence of'xylene or anequivalent water-'- insoluble solvent may mask thepoint at which a solvent-free product on mere dilution in'atest tube exhibits self-emulsification. For thisreason, if it is desirable to determine the approxi mate pointwhere self-emulsificationbegins, then it is better to eliminate thexylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylenefree resultant may show initial or incipient nydrophile properties, whereas in presence of'xyle'rie such properties would not be noted. In other cases, the first objective indication of hydrophile properties maybe the'capacity of the'mat'e'rial to emulsify an insoluble solvent such as Xylene. It is to be emphasized thathydrophile roperties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of com-5 mon electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsifica tion test may be used to determine ran es of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

In light of what has been said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as to the variation in the efiectivene'ss of various alkylene oxides, and most particularly of all ethylene oxide, to introduce hydrophile character, it becomes obvious that there is a wide variation in the amount of alkylene oxide employed, as long as it is at least 2 moles per phenolic nucleus, for producing products usefulfolf the practice of this invention. Another variation is the molecular size of the resin chain resulting from reaction between the difunctional phe nol and the aldehyde such-asformaldehyde. It is well known that the size and nature or struc-' ture of the resin polymer obtained varies somewhat with the conditions of reaction, the pro-' portions of reactants, the nature of the catalyst, etc.

Based on molecular weight determinations, most of the resins prepared as herein described, particularly in the absence of a secondary heating step, contain 3 to 6 or '7 phenolic nucleiwith approximately 4 or 5 /2 nuclei as an average. More drastic conditions of resinification"- yield resins of greater chain length. 'Such' more intensive resinification is a conventional procedure and may be employed if desired. Molecular weight, of course, is measured by any suitable procedure, particularly by cryoscopic methods; but using the same reactants and using more drastic conditions of resinification one usually finds that higher molecular weights are indicated by higher melting points of the resins and a tendency to decreased solubility. See what has been said elsewhere herein in regard to a's'ec-j ondary step involving the heating of a resin with or without the use of vacuum.

' We have previously pointed out that either an alkaline or acid catalyst is advantageously used in preparing the resin. A combination of catalysts is sometimes used intwo stages; .for-inp' stance, an alkaline catalyst is sometimes employed in a first stage, followed by neutralization and addition of a small amount of acid catalyst in a second stage.- It is generally believed that even in the presence of an alkaline catalyst, the number of moles of aldehyde, such as formaldehyde, must be greater than the moles of phenol employed in order to introduce methylol groups in the intermediate stage. There is no indication that such groups appear in the final resin if prepared by the use of an acid catalyst. It is possible that such groups may appear in the finished resins prepared solely with an alkaline catalyst; but we have never been able to confirm this fact in an examination of a large number of resins prepared by ourselves. Our preference, however, is to use an acid catalyzed resin, particularly employing a formaldehyde-to-phenol ratio of 0.95 to 1.20 and, as far as we have been able to determine, such [resins are free from methylol groups. As a matter of fact, it is probable that in acid-catalyzed .resinifications, the methylol structure may appear only momentarily at. the very beginning of the reaction and in all probability is converted at once into a more complex structure duringthe intermediate stage.

One procedurewhich can be employed in the use of a new resin to prepare polyhydric reactants for use in thepreparation of compounds employed in the present invention, is to determine the hydroxyl value by the Verley-Bdlsing method or its equivalent. The resin as such, or in the form of a solution as described, is then treated with ethylene oxide in presence of 0.5% to 2% of sodium methylate as a catalyst in step-wise fashion. The conditions of reaction, as far as time or per cent are concerned, are within the range previously indicated. With suitable agitation the ethylene oxide, if added in molecular proportion, combines within a comparatively short time, for instance a few minutes to 2 to 6 hours, but in some instances requires as much as 8 to 24 hours. A useful temperature range is from 125 to 225 C.- The completion of the reaction of each addition of ethylene oxide in step-wise fashion is usually indicated by the reduction or elimination of pressure. An amount conveniently used for each addition is generally equivalent to a mole or two moles of ethylene oxide per hydroxyl radical. When the amount of ethylene oxide added is equivalent to approximately 50% by weight of the original resin, a sample is tested for incipient hydrophile properties by simply shaking up in water as is, or after the elimination of the solvent if a solvent is present. The amount of ethylene oxide used to obtain a useful demulsifying agent as a rule varies from 70% by weight of the original resin to as much as five or six times the weight of the original resin. In the case of a resin derived from para-tertiary butylphenol, as little as 50% by weight of ethylene oxide may give suitable solubility. With propylene oxide, even a greater molecular proportion is required and sometimes a resultant of only limited hydrophile properties is obtainable. The same is true to even a greater extent with butylene oxide. The hydroxylated alkylene oxides are more effective in solubilizing properties than the comparable compounds in which no hydroxyl is present.

Attention is directed to the fact that in the subsequent examples reference is made to the stepwise addition of the alkylene oxide, such as ethylene oxide. It is understood, of course, there is no jection to the contin ous addition of alkylene oxide until the desired stage of reaction is reached. In fact, there may be less of a hazard involved and it is often advantageous to add the alkylene oxide slowly in a continuous stream and in such amount as to avoid exceeding the higher pressures noted in the various examples or elsewhere.

It may be well to emphasize the fact that when resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is a comparatively soft or pitch-like resin at ordinary temperatures. Such resins become comparatively fluid at to C. as a rule, and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

What has been said previously is not intended to suggest that any experimentation is necessary to determine the degree of oxyalkylation, and particularly oxyethylation. What has been said previously is submitted primarily to emphasize the fact that these remarkable oxyalkylated resins having surface activity show unusual properties as the hydrophile character varies from a minimum to an ultimate maximum. One should not underestimate the utility of any of these polyhydric alcohols in a surface-active or subsurface-active range without examining them by reaction with a number of the typical acid herein described and subsequently examining the resultant for utility, either in demulsification or in some other art or industry as referred to elsewhere, or as a reactant for the manufacture of more complicated derivatives. A few simple laboratory tests which can be conducted in a routine manner will usually give all the information that is required.

For instance, a simple rule to follow is to prepare a resin having at least three phenolic nuclei and being organic solvent-soluble. Oxyethylate such resin, using the following four ratios of moles of ethylene oxide per phenolic unit equivalent: 2 to 1; 6 to 1; 10 to 1; and 15 to 1. From a sample of each product remove any solvent that may be present, such as xylene. Prepare 0.5% and 5.0% solutions in distilled water, as previously indicated. A mere examination of such series will generally reveal an approximate range of minimum hydrophile character, moderate hydrophile character, and maximum hydrophile character. If the 2 to 1 ratio does not show minimum hydrophile character by test of the solventfree product, then one should test its capacity to form an emulsion when admixed with xylene or other insoluble solvent. If neither test show the required minimum hydrophile property, repetition using 2 /2 to 4 moles per phenolic nucleus will serve. Moderate hydrophile character should be shown by either the 6 to 1 or 10 to 1 ratio. Such moderate hydrophile character is indicated by the fact that the sol in distilled water within the previously mentioned concentration range is a permanent translucent sol when viewed in a comparatively thin layer, for instance the depth of a test tube. Ultimate hydrophile character is usually shown at the 15 to 1 ratio test in that adding a small amount of an insoluble solvent, for instance 5% of xylene, yields a product which will give, at least temporarily, a transparent or translucent sol of the kind just described. The formation of a permanent foam, when a 0.5% to 5.0% aqueous solution is shaken, is an excellent test for surface activity. Previous reference has been made to the fact that other oxyalkylating agents may require the use of increased amounts for the terminal units.

2'3" etalkylene. oxide. -I-l'wever, if :one does noteven care to go to the trouble of calculating molecular Weights, one can simply arbitrarily prepare, compounds containing ethylene oxide equivalentto about 50% to 75% by weight,.for example 65% by weight, or" the resin to be oxyethylated; a second example using approximately 280% to ,300%' by weight, and a third example using about 500-.% to

750% by weight, to explore the range ofrhydrophile-hydrophobe balance. A practical examination of the faotorof 'oXyalkylation level can be made by a very simple test using a pilot plant autoclave having a ca-pacity'of about 16 to gallons as hereinafter de-; scribed. Such laboratory-prepared routine compounds can then be tested for solubility and, gen-. erally speaking, this is all that is. required to. give asuitable variety covering the hydrophile-hydrophqbe. range. All these tests, as stated, are intended to be routine tests and nothing .more. They are intended to teach a person, even though unskilled in oxyethylation or oxyalkylation, how to prepare in a perfectly arbitary manner, a series of compounds illustrating the hydrophile-hydrophobe range.

,If one purchases a thermoplastic or fusible resin on the open market selected from a suitable number which are available, one might have to make certain determinations in order to make the quickest approach to the appropriate oxyalkylation range. For instance, one should know (a) the' molecular size, indicating the number ofphenolic units; (b) the nature of the aldehydic residue, which is usually CH2; and c) the nature of the substituent, which i usually butyl, amyl, or phenyl. With such information one is in substantially the same position as if one had personallylmade the resin prior to oxyethylation.

f For instance, the molecular weight of the internal. structural units of the resin of the followingv over simplified formula:

is given approximately by the formula: Molqwt. of phenol 2) plus mol. wt. of methylene. or substituted methylene radical. The molecular weight. of the resin would be n times the 'value for the internal limit plus the values The left-hand terminal unitlof the above structural formula, it' will be seen, is identical with the recurring internal unit except that it has one extra hydrogen. The right-hand terminal unit lacks the methylene bridge element. Using one internal unit of a resin as the basic element, a resins' molecular weight is given approximately by taking (it plus 2) times the weight of the internal element. Where the resin molecule has only 3 phenolic nuclei as in the structure shown, this calculation will be in error by several per cent; but as' it grows larger, to contain 6, Ber 12 phenolic nuclei, the formula comes to be rrore than satisfactory. Using such an approximate weight, oneneed only introduce; ror: example,

two molalweights of ethylene oxide or slightly more, per phenolic nucleus, to .produce-.a prod-. not of minimal vhydrophile character. Further-I oxyalkylation gives enhanced hydrophile character. Althoughv we have prepared and tested a large number of oxyethylated productsofthe; type described herein, we have found no instance where the use of less than 2 moles offethylene oxide per phenolic nucleus gave desirable; products. H

Example 112 through 18b, and the tables which appear in 'columns5lthrough-56 toxourz said Patent 2,499,370 illustrate oxyalkylation: products from resins which are useful as inter mediates for producing the este'rified products,

used in accordance with the present application, such examples giving exact andcomplete. details; for carrying out the'oxyalkyl'ation procedure;

The resins, prior to oxyalkylation, vary/from tacky, viscous. liquids tohard, high-melting solids. Their color varies from .a "light yellow through amber, to a deep red or even Ialmost black. In the manufacture of resins, particularly hard resins, as the reaction progresses'the' reaction mass frequently goes through a liquid state to a sub-resinous or semi-resinous state; often characterized by being tacky or sticky,'.to a final comp-ete resin. As the:resinisisubjiected to oxyalkylation these same physical changes tend to take place in reverse. If one starts with a solid resin, oxyalkylation tends tov makeui'ttacky or se'mi-resinousand furtheroxyalkyla-i tion makes the tackiness'disappearand. changes: the product to a liquid. Thus, asthe" resin. .is'

oxyalkylated it decreasesin viscosity, that: is,"-

beconies more liquid 'or changes fromv a solidv to..a liquid, particularly when-it is converted'to'th'ewater-dispersible or Water-soluble stage. The color of the" oxyalkylated derivative is usually considerably lighter than the original product from Which it is made, varying from a pale straw color to an amber or reddish amber. The viscosity usually varies from thatof anoil, likecastor oil, to that of a thick viscous sirup. Some products are Waxy. The presence of a' solvent, such as 15% xylene or the like, thins the viscosity considerably and alsoreducesthe color in dilu tion. No undue significance need be attached-to the color for the reason that if the same-come:- pouhd is prepared in glassand in iron, the latter usually has somewhat darker color. If the resins are prepared as customarily employed in varnish resin manufacture; i. e.,- a procedure that 'exeludes the presence of oxygen during the1re'sini'-- fication and subsequent cooling of the resin; then of course the initial resin is much lighter. in color. We have employed some resins which initially are almost water-white and also yield' a lighter colored final product.

Actually, in considering the ratio'of alky lerie' oxide to add, and we have previously pointedo'ut that this can be pre-determined using laboratory tests, it is our actual preference from a practical standpoint toinake tests on a smau' notpnut scale. Our reason for so doing is that we make one run. and onlyone, and that we have acornplete series which shows "the progressive effect of introducing the oxyalkylating agent; for instance, the ethyleneox'y'radicals Our preferred procdure is as follows: We prepare asuitable resin,-or' for that matter, purchase it in theopen market. We employ 8 pounds of resin and 4; pounds of xy-' lene and place the resin and xylene in a suitab1e autoclave with an open reflux condensen We-pre fer to heat and" stiruntil the solution is complete =We have pointed out that soft resins which are fluid or semi-fluid can be readily prepared in various ways, such as the use of ortho-tertiary amylphenol, ortho-hydroxydiphenyl, ortho-decylphenol, or by the use of higher molecular weight al dehydes than formaldehyde. If such resins are used, a solvent need not be added but may be added as a matter of convenience or for comparison, if desired. We then add a catalyst, for instance, 2% of caustic soda, in the form of a 20% to 30% solution, and remove the water of solution or formation. We then shut off the reflux condenser and use the equipment as an autoclave only, and oxyethylate until a total of 60 pounds of ethylene oxide have been added, equivalent to 750% of the original resin. We prefer a temperature of about 150 C. to 175 C. We also take samples at intermediate points as indicated .in the following table: a

Pounds of Ethylene Percentages Oxide Added per 8-pound Batch Oxyethylation to 750% can usually be completed within 30 hours and frequently more quick y.

The samples taken are rather small, for instance, 2 to 4 ounces, so that no correction need be made in regard to the residual reaction mass. Each sample is divided in two. One-half the sampie is placed in an evaporating dish on the steam bath overnight so as to eliminate the xylene. Then 1.5% solutions are prepared from both series of samples, i. e., the series with xylene present and the series with xylene removed.

Mere visual examination of any samples in solution may be sufficient to indicate hydrophile character or surface activity, i. e., the product is -soluble, forming a colloidal sol, or the aqueous solution foams or shows emulsfying property. All these properties are related through adsorption at the interface, for example, a gas-liquid interface or a liquid-liquid interface. If desired, surface activity can be measured in any one of the Y usual ways using a Du Nouy tensicmeter or dropping pipette, or any other procedure for measur- -lng interfacial tension. Such tests are conventional and require no further description. Any

compound having sub-surface-activity, and all derived from the same resin and oxyalkylated to I a greater extent, i. e., those having a greater 'pro portion of alkylene oxide, are useful as polyhydric reactants for the practice of this invention.

Another reason why we prefer to use a pilot plant test of the kind above described is that we can use the same procedure to evaluate tolerance towards a trifunctional phenol such as hydroxy- "benzene or metacresol satisfactorily. Previous reference has been made to the fact that one can conduct a laboratory scale test which will indicate whether or not a resin, althoughsoluble in 'solvent, will yield an insoluble rubbery product,

"'i. e., a' product which is neither hydrophile nor Js'urface-active, upon oxyethylation, particularly 26 extensive oxyethylation. It is also obvious that one may have a solvent-soluble resin derived from a mixture of phenols having present 1% or 2% of a trifunctional phenol which will result in an insoluble rubber at the ultimate stages of oxyethylation but not in the earlier stages. In other words, with resins from some such phenols, addition of 2 or 3 moles of the oxyalkvlating agent per phenolic nucleus, particularly ethylene oxide, gives a surface-active reactant which is perfectly satisfactory, while more extensive oxyethylation yields an insoluble rubber, that is, an unsuitable reactant. It is obvious that this present procedure of evaluating trifunctional phenol tolerance is more suitable than the previous procedure.

It may be well to call attention to one result which may be noted in a long drawn-out oxyalkylation, particularly oxyethylation, which would not appear in a normally conducted reaction. Reference has been made to cross-linking and its effect on solubility and also the fact that, if carried far enough, it causes incipient stringiness, then pronounced stringiness, usually followed by a semi-rubbery or rubbery stage. Incipient stringiness, or even pronounced str nginess, or even the tendency toward a rubbery stage, is not objectionable so long as the final prod ct is still hydrophile and at least sub-surface-active. Such material frequently is best mixed with a polar solvent, such as alcohol or the like, and preferably an alcoholic solution is used. The point which we want to make here, however, is this: Stringiness or rubberization at this stage may possibly be the result of etherification. Obviously if a difunctional phenol and an aldehyde produce a non-cross-linked res n molecule and if such molecule is oxyalkylated so as to introduce a p uralitv of hydroxyl groups in each molecule, then and in that event if subsequent etherificetion takes place, one is going to obtain cross-linking in the same general way that one would obtain cross-linking in other resinification reactions. Ordinarily there is little or no tendency toward etherification during the oxyalkylation step. If it does take place at all, it is only to an insignificant and undetectable degree. However, suppose that a certain weight of resin is treated with an e ual wei ht of, or twice its Weight of, ethylene oxide. This may be done in a comparatively short time, for instance,

of ethylene oxide employing the same temperature, then etherification mi ht cause stringiness or a suggestion of rubberiness. For this reason if in an exploratory experiment of the kind previously described there appears to be any stringiness or rubberinessit may be well to repeat the experment and reach the intermediate stage of oxyalkylation as rapidly as possible and then proceed slowly beyond this intermediate stage. The

entire purpose of this modified procedure is to cut down the time of reaction so as to avoid etherification if it be caused by the extended time period.

It may be well to note one peculiar reaction ';sometimes noted in the course of oxyalkylation,

particularly oxyethylation, of the thermoplastic resins herein described. This effect is noted in a case where a thermoplastic resin has been oxyalkylated, for instance, oxyethylated, until it gives a perfectly clear solution, even in the presence of =-deoomposes and an .oxyalkylated resin represent -=irig alower degree of oxyethylationand'a.less *soluble one, is generated and'a cyclic polymerof ethylene oxide is produced, indicated thus:

T hisyfact, of course, presents no diffi'culty for the freason'that oxyalkylation can be conducted in each instance stepwise, or at-a gradual rate, and s'arnples' taken at short intervals so as to arrive at" a point where optimum surface activity or "hydrophile character isobtained-if desired; for products for use as polyhydric reactantsin the practice of this invention, thi is notnecessary and; in fact, may be undesirable, i. e., reducetlie j 'eflicienoy of the product. i

We do not know to what'gaxtentoxyalkylation Qproduces uniform distribution in regard to pheinolic 'hydroxyls present in the resin molecule.- In lsome instances, of course, such distribution can ff n ot' be-uniform for the reason that We have not specified that the molecules of ethylene oxide, for example, be added in multiples of the units present in the resin molecule. This maybe illustrated in the following manner: Suppose the resin h ppens to have fiveplienolic nuclei. If a minimum of two moles of ethylene oxide perph'enolic nucleus are added, this would '-'-mean an addition of 10 moles of ethylene oxide, 'butsuppose that one added llmoles of ethylene oxide, or 1 2, or 13, or 14 moles; obviously; even assuming the most uniform distribution possible, some of the polyethyleneoxy radicals would con- -tain 3 ethyleneoxy units andisome would contain 2. Therefore, it is impossible to specify uniform distribut on in regard to the-entrance of the eth- "ylene oxide or other oxyalkylating agent:- For -that -matter', if one weret'o introducey25*mo'lesof ethylene oxide thereis no way to becertain' that all chainsof ethyleneoxy units would have 5iunits "there-m'ight be some'having, fo example", 4 and GEunits; error that matter 3 ort'lfunits; Nor is there any basis for: assu ming, that-the number? of 'molecules .of' the .ox-yal-kylating agent-added to each of the molecules of'the, resin-is thev same,

In-regard to solubility of the -resins andthe :oxya lkylated compounds, and for that matter rderiva-tives of the latter, the following should be noted". should be-non-reactive to the alkylene oxide em- ".1 rrloyedi .Ihis limitati n does: noiz-apn vridsol- In oxyalkylation, any solvent employed rventsused. in seryoscopic determinations "for: ion- --V' l0L lS1"le &S01-1S.i Attention. is directed to the'xfact that? various; organic solvents may be employed to-lverify that the resin is organic solvent-soluble.

Such, solubility testmerely charactcrizes the "resin; The particular solvent usedin such test :may not be suitable for a molecular weight :de-

termination and, likewise, the solvent used in determining molecular weight may not'besuitable as 1 a solvent during .oxyalkyl'ation. For solution of-:.';theioxyalkylated compounds, or their deriva- 1. H engowgn omn q nQowrmomn [0%.

tives agreat variety of solvents may be employed,

suchasaloohols, etheralcohols, cresols', phenols,

ketones, esters; etc.-, alone or with the addition of water. Some of these are mentioned hereafter; We; preferithe use of benzene or diphenylamine as a solvent in making cryoscopic measurements. The most satisfactoryresins are those which are solublein xylene or-ithe like, rather than those which are soluble only in: some other solvent containing'elrments other than carbon and hydrogen, forv instance, oxygen or chlorine. Such solvents are usually polar, semi-polar, or slightly polar in nature compared'with xylene, cymene, etc.

Reference to ,cryoscopiemeasurement is 110011 cerned-with the; useof benzene. or other suitable compound as asolvent. Such method will show thatconventional resins obtained, forexample,

irom paraetertiary amylphenol and formaldehyde in presence of an 'acid catalyst, will have a: molecular weight indicating 3, 4; 5 or some- What greater number of structural units per molecule. If more drastic conditions of resinification are employed or if such low-stage resin is subjected to a vacuum distillation-treatment as previously d. scribed, one, obtains a resin of a. distinctly higher molecular weight. Any molecular. weight determination used, Whether ,cryoscopic measurement or otherwise, other than the conventional cryoscopic one employing benzenr, should be checked so as to insurev that Frequently all that is necthe same aldehyde under oOl ditions; to insurerdimeri a n- Asto h ri pa t onof such d mers 'iromsubstituted phenols, see, Carswell, Phenollla'sts, pa e e1; The-inc ea d visc ty, r sinouscharacter, and decreased solubility, etc., of the higher polymers in comparison with the dimer, frequ ntly are all that is required toestablish that the resin conta-insB. ormore structural units I per molecule.

Ordinarily; the oxyalkyla-tion is carried outin iautoclaves provided with agitators or stirring devices." We have found that the speed of the ag-itation markedly influences the, reactiontime.

In some cases, the change from slow speed, agitation, for exampla-in a laboratory autoclave a at on w th a stirr r pe a-fi er a spee of 69.1 .952.903. .BrMi tohiahsnee agitation; with 'viously.

ucts by procedures employing comparatively slow speed agitation, give suitable hydrophile products when produced by similar procedure but with high speed agitation, as a result, We believe, of the reduction in the time required with consequent elimination or curtailment of opportunity 2 for curing or etherization. Even if the formation of an insoluble product is not involved, it is frequently advantageous to speed up the reaction, thereby reducing-production time, by increasing agitating speed. In large scale operations, we have demonstrated that economical manufacturing results from continuous oxyalkylation, that is, an operation in which the alkylene oxide is continuously fed to the reaction vessel, with high sped agitation, i. e., an agitator operating at 250 to 350 R. P. M. Continuous ,oxyalkylation, other conditions being the same, is more rapid than batch oxyalkylation, but the latter is ordinarily more convenient for laboratory operation.

Previous refer nce has been made to the fact that in preparing esters or compounds of the kind herein described, particularly adapted for demulsification of water-in-oil emulsions, and

make a complete exploration of the wide variation in hydrophobe hydrop'hile balance as preof the oxyalkylated resins is imparted, as far. as

the range of variation goes, to a greater or lesser' extent to the herein described derivatives. This In ans-that one employing the present invention should take the choice of the most suitable derivative selected from a number of representative compounds, thus, not only should a variety of resins be prepared exhibiting a variety of oxyalkylations, particularly oxyethylations, but also a variety of derivatives. This can be done conveniently in light of what has been said pre- From a practical standpoint, using pilot plant equipment, for instance, an autoclave having a capacity of approximately three to five gallons. We have made a single run by appropriate s lections in which the molal ratio of resin equivalent to ethylene oxide is one to one, 1 to 5 l to 10. 1 to 15, and 1 to 20. Furthermore, in making these particular runs we have used continuous addition of ethylene oxide. In the continuous addition of ethylene oxide we have employed either a cylinder of ethylene oxide without added nitrogen, provided that the pres sure of the ethylene oxide was sufiiciently great to pass into the autoclave, or else we have used an arrangement which, in essence, was the equivalentFof an ethylene oxide cylinder with a means for injecting nitrogen so as to force out the ethylene oxide in the manner of an ordinary seltzer bottle, combined with the means for either weighing the cylinder or measuring the ethylene oxide used volum1trically. Such procedure and arrangement for injecting liquids is, ofcourse, conventional. The following data sheets exemplify such operations, i. e., the combination of both continuous agitation and taking samples so as to give five different variants in oxyethyla tion. In adding ethylene oxide continuously, there is one precaution which must be taken at all times. The addition of ethylene oxide must stop immediately if there is any indication that reaction is stopped or, obviously, if reaction is not started at the beginning of the reaction period. Since the addition of ethylene oxide is invariably an exothermic reaction, Whether or not reaction has taken place can be judged in the usual manner by observing (a) temperature rise or drop, if any, (b) amount of cooling water or other means required to dissipate heat of reaction; thus, if there is a temperature drop without the use of cooling water or equivalent, or if there is no rise in temperature without us ing cooling Water control, careful investigation should be made.

In the tables immediately following, we are showing the maximum temperature which is usually the operating temperature. In other words, by experience we have found that if the initial reactants are raised to the indicated tem perature and then if ethylene oxide is added slowly, this temperature is maintaimd by cooling water until the oxyethylation is complete, We have also indicated the maximum pressure that we obtained or the pressure range. Likewise, we have indicated the time required to inject the ethylene oxide as well as a brief note as to the solubility of the product at the end of the oxyethylation period. As one period ends it will be noted We have removed part of the oxyethylated mass to give us derivatives, as therein described; the rest has been subjected to further treatment. All this is apparent by examining the columns h. aded Starting mix. Mix at end of reaction, Mix which is removed for sample, and Mix which remains as next starter.

The resins employed are prepared in the manner described in'Examples 1a through 103a of our said Patent 2,499,370, except that instead of being prepared on a laboratory scale they were prepared in 10 to l5-gallon electro-vapor heated synthetic resin pilot plant reactors, as manufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, and completely described in their bulletin No. 2087 issued in 1947, with specific reference to specification No. 71-3965.

For convenience, the following tabl:s give the numbers of the examples of our said Patent 2,499,370 in which the preparation of identical resins on laboratory scale are described. It is understood that in the following examples, the change is one with respect to the size of the operation.

The solvent used in each instance was xylene. This solvent is particularly satisfactory for the reason that it can be removed readily by distilla tion or vacuum distillation. In these continuous experiments the speed of the stirrer in the autoclave was 250 R. P. M.

In examining the subsequent tables it will be not d that if a comparatively small sample is taken at each stage, for instance, to one gallon, one can proceed through the entire molalstage of 1 to 1, to 1 to 20, without remaking at any intermediate stage. This is illustrat d by Example 10417. In other examples we found it desirable to take a larger sample, for instance, a B-gallon sample, at an intermediate stage. As a result it was n cessary in such instances to start with a new resin sample in order to prepare sufficient oxyethylated derivatives illustrating the latter stages. Under such circumstances, of course, the earlier stagzs which had been previously prepared were by-passed or ignored. This is illustrated in the tables where, obviously, it shows that the starting mix was not removed from a previous sample.

25 51525015; 3T 7 '0 Phnol'fbr resinr Pd'riairtiary timy'lphenol Aldehyde fofresinr.Farmaldehycle.- 1500s,. 194s I V [Resinmade in pilot plant size batch, approximately 25 pounds, corresponding to 342.01 Patent-2,499,320but xhis batch designated 1041.1

' Mix Which is Mix Which Re.- Starting Mix figg figg of Removed for. I mains as Next Sample 7 Starter Max M Time Pressure- Tempgrahrs. Solubxhty i b s. Ifibs. Lbs l b s. Ifibs. Lbs I m I bs. Lbs 'ISJbIs; Ibs.

oesoes- 0- es- 0- esvent in Eto vent in I Eto vent in vent i1 7 Eto First Stage Resin to EtO Molal ,Ratio 1:1- 14. 715.75 0 14. 25 15. 75 4. 0 3. 3. 1. 0 10. 9 12.1 3.0 80 150 $4 I Ex. N0; 1040".-. I setand Stage 3 summon Q .1 I M :5 '10 9 12.1 3.0: 10.9 12.1 15.25 3.77 4.17 5.31 7. 13 7. 93 9. 94' 158 ST 7" Third Stage Besinto 1100.--. (I Molal Ratio 1:10. 7. '13 7. 93 9. 94 7. 13 7. 93 10. 69 3. 29 3. 68 9.04 3. 84 4. 25 10. 65 60 1 173 $51 FS EX..N 02'106b Fourth Stage' Resin to EtO... M01211 Ratio *1:15 3. 84 4. 25 10. 65 3. 84 .4. 25 16. 15 2. 04 2. 21 8. 55 1. 2. 04 a 7. 60 220 160 6 RS EX. N0.,107b

Fifth Stage Resin to Et0 M0131 Ratio 1:20; 1.80 2.04 7. 60 1. 80 2.04 10.2 150 j M; 1 Q5 Ex. No. 1080;..-

insoluble. ST. Slight, tendency toward "beoomiugsoluble. F 5 ,=.Fairly soluble, R5 Readily soluble. QS .=.Quite soluble,

H Phenol for resin. Nonylphenal. Aldehyde. for resin:.. For.maldahygie. I Date, June 18,1048

[Resin made in pilot plant size batch, approximately 25 p0unds,'c0rresponding to 70a of Patent 2,499,370 but this batch designated 10911.]

. Mix Which is Mix Which Re- 1 Starting Mix 35 32 of Removed for mains as Next.

Sample Starter Max. Max. Time 7 Pressure Temp erahrs f Solubility 'Lbs. Lbs. Lbs Lbs. Lbs. T hs Lbs. Lbs. Lbs Lbs. Lbs. Lbs, sq; Sol- Res- Sol- Resfi Sol- Resc 301- Resvent in vent in vent in vent in; i

FirstStage Resin to EtO M0131 Ratio 1:1. 15 0 15. 0 0 15. 0 l5. 0 3' 5. 0 5. 0 1. ,0 10.0 10.0 2. 0 50 150 1% ST E3;No.109b

Second Stage Resin to EtO Molal Ratio 1:5; 10 10 2.0 10 10 9.4 2:72 2. 72 2.56 7.27 7.27 6.86 100 147 2 DT- ExuNo. 1,100... I v I 5,. Third Stagev v ResintoEt0; I v V w Molal Ratio 1: 10- 7 27 7. 27 6. 86 7. 27 7. 27 '13. 7 4. 16 4. 16 7.. 68 3. 15 j 3.15 5.95 a" 1, ,5 1% S..-

o. .111b y Fiiwrthsi a R'esinioEtOl'... 1 1 i 1510151113110 1:15. 3. 15 3.15 5.95 3.115 Q). 15 8.95 1.05 1.05 2.95.. 2.10 2110. 6.00 220 174. 2%.v S, 4 EX-.. 0-.

L Fifth- Stage;

Resin to'EtO i Mala] Ratio 1:20- 2.10 2.10 6. 00 2. 10 2.10 8.00 ...,.v 2.20 18.3. 95 S. EX. N0. 113b i S"=So1ub1e. ST=S1ight tendency toward solubility. DT=Definitetendencymwardsolubility. VS=Very soliibl I I 2,542,013 33 34 Phenolfor resin: Para-oe'tylphenol Aldehyde for resin: Formaldehyde Date, June 23. 24, 1948 [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to So of Patent 2,499,370 but this batch designated 114m] Mix Which is- Mix Which Re- Starting Mix fi g gg of Removed for mains as Next Sample Starter I Pressure Temp eraa g Solubility I b s; Ifibs. Lbs I b S. Ifibs. Ibis. abs. Lbs gills. gm. Lbs

0- es- 0- eses 0- ese I vent in Eto vent in Eto vent in Eto vent in Eco First Stage' Resin to 12150.... MolalRatio 1:]; 14; 2 15.8 0 14. 2 15.8 3'. 3.1 314 1 0'. 1'1. 1. 12.4 2. 5 l 50 150 1%: NS Ex. N0. 1141).--

Second Stage Resin to EtO...- M0121 Retio1:5- 11 .1 12. 4 215 11. 1 12.4 112. 5 7.0 7.82 7.88 4.1 4.58 4.62 106 171 16 SS Ex. No. 11512"--- I Third Stage Resin to EtO M0181 Ratio 1:10. 6 64 7.36 0 6. 64. 7.36 15. 0. 190 1% S Ex. No. 116b Fourth Stage Resin to EtO.. Molal Ratio 1:1 4 4D 4. 9 0' 4.4 4. 9 .14. 8. 400 160 56 VS Ex. No.117b...

Fifth Stage Resin to EtO M0131 Ratio 1:20; 421 4.58 4.62 4.1 4.58 18. 260 172 5!; VS Ex. No. 118b- I I S Soluble. N S =Not soluble. SS somewhztsoluble. VS.=Very'so1ub1e.

Phenol for'resiw." M enthylphenol Aldehyde for resin: Formaldehyde Date, July 843, 1948 [Resinlmadedm pilot plantsize batch, approximately 25 p0unds, corrospondingto 69a of- Patent 2,499,370 but this batch designated 119a.]

' r Mix Whiclfis MirWhichRe- Starting Mix ggg g g of Y 5 Removed for mains as Next 1 Sample Starter Max. Max. Time I Pressure Tempgra hrs Solubility gbiq gm Lbs fi I IIbSI s I g LB SI LU S lbs. sq. in. til-1'8, C.

0- es- 0- es; 0 es 0; vent in Eto vent in Em vent in' Eto vent in Et First Stage Resin to EtO I Mulalllatioihl 13 65 16.35 0 13. 65 116.35 3.0 9355111145 2.'1 4L1 4E9 039 c 60- 1% NS Ex. No. 119b.----

Second Stage Resin to EtO. I MolalzB/atio 1'5 10' 12 0. 10 12 10.75 43-52 5242. 4.81 5.48 6. 58 5. 94 140 1%: S Ex. No:.120b I Third Stage:

Resin t0 EtO Molal .RatiodzlO. 5 48 6.58 5.94 5.48 6.58 10.85 v 90 160 M S Ex. No. 121b....-

Fourth Stage;

Resin to EtO I M0lal ,Ratio1:15- 4.1 4.9 019 4.1 4. 9 113.15 s l 180 171 1%: VS Ex. N0.122b

Fifth Stage Resin to EtO I MolaLR-atjo 1220; 3. 10 3.72 01 68 3.10 3.72213. 43 320 VS Ex.No. 1231)"--- l S =Soluble. NS =N'ot soluble. VS=Very soluble.

Phenol for resin: Para-secondary butylphenol Aldehyde forresin: Formaldehyde Date, July 14-15, 1948 1 [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 21 of'Patent 2,499,370 but this batch designated 12411.1

, 1 Mix Which is Mix Whlch Re- 1 Starting Mix figg ggg of Removed for mains as Next Sample Starter Max. Max. Time Pressure Temp erahm Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs.

Lbs. Lbs. Lbs. Lbs. Sol- Res- Eto S01- Res- Eco Sol- Res- Etc 801- Res- Eto vent in vent in vent in vent in First Stage Resin to EtO Molal Ratio 1:1" 14.45 15.55 0 14.45 15.55 4.25 5.97 6.38 1.75 8. 48 9. 17 2.50 60 150 91: 1 NS Ex. N 0. 124b.

Second Stage Resin to EtO. Molal Ratio 1:5 8.48 9.17 2. 50 8. 48 9.17 16.0 5.83 v 6.32 11.05 2.65 2.85 4.95 95 188 ,6 SS Ex. N0.125b 1 Third Stage Resin to EtO Molal Ratio 1:10 4.82 5.18 0 4. 82 5.18 14.25 400 183 16 8 Ex. No. 126b 7 Fourth Stage Resin to EtO Molal Ratio 1:15- 3.85 4.15 0 3.85 4.15 17. 0 3.10 4.17 10. 1'3 120 180 VS Ex. No. 1270 Fifth Stage Resin to Et0 Molal Ratio 1:20- 2.65 2.85 4.95 2.65 2.85 15.45 80 170 M2 VS Ex. No. 12812......

S=So1uble. NS=Not soluble. SS=Somewlmt soluble. VS=Very soluble.

Phenol for resin: Men'thyl Aldehyde for resin: Pr opionaldehyde Date, August 12-13, 1948 [Resin made on pilot plant size batch, approximately pounds, corresponding to 81a of Patent 2,499,370 but this batch designated 12911.]

- Mix Which is Mix Which Re- Starting Mix figg ggg of Removed for mains as Next Sample Starter Max Ma Time Pressure Temp erahrs Solubility gels. gbs. Lbs r b s. m. Lbs lsibls. r bs. Lbs Isibls. Ifibs. Lbs

0 eso eso eso esvent in Eto vent in Eto vent in Eto vent in Eto First Stage Resin to EtO- p Molal Ratio l:1 12.8 17.2 12.8 17.2 2.75 4.25 5.7 0.95 8. 11.50 1.80 X; Not soluble.' Ex. N0. 129!) Second Stage Resin to EtOQ--. Molal Ratio 1:5 8. 55 11.50 1.80 8.55 11; 50 9.3 4.' 78 6.42 5.2 3.77 5.08 4.10 100 3% Somewhat Ex. No. 13% soluble.

Third Stage Resin to Et0 Molal Ratio 1:10- 3.77 5.08 4.10 3.77 5.08 13.1 100 182 M2 Soluble. Ex. No. 131b Fourth Stage Resin to Et0 Molal Ratio 1:15 5.2 7.0 5.2 7.0 17.0 3.10 4.17 10.13 2.10 2.83 6. 87 200 182 Very soluble. Ex. N0. l32b- Fifth Stage Resin to EtO V Molal Ratio 1:20- 2.10 2.83 6.87 2.10 2.83 9.12 90 150 $5 Verysoluble. Ex. No. 133m-.-"

Date, August 21-31 Phenol .r .in-' am-. i ry amy ph nal Al e yd /fa resi Fu f [Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 42a of Patent 2,499.370 but thisbat ch designated as 134a.]

- Mix Which is Mix Which Re- Starting Mix g figg 9f 9 Removed for mains'as Neg;

Sample Starter Max Max. Pressure Tempgraag? Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. s01- Resgg Sol- Res- 801- Res- 52% s Resgvent in vent in vent in vent in First Stage Resin to Et0 Molal Ratio 1:1; 11. 2 18.0 11. 2 18.0 ,3. 5 2. 75 ,4. 4 0.85 8.45 13. 6 '12. 65 120 "135 1- Not soluble.

EX. N0. 134!) Second Stage Resin to EtO. IVIolal Ratio 1:5 8. 13. 6 2. 65 8. 45 13. 6 12. 65 5.03 3.12 .7. 3.42 5. 48 5. 10 110 150 $4 Somewhat Ex. N0. 135b soluble.

Third Stage Resin to 111.0..-" 3 Molal Ratio 1:10.. 4. 5 8.0 4. 5 8. 0 14.5 2. 45 4. 35 7. 99 2. 05 3. 65 6.60 180 163 $5 Soluble. EX. N0. 136b Fourth Stage Resin to EtO 1 Mola1Ratio1:15 3.42 5. 48 5.10 3.42 5. 48 15.10 1 180 188 $5 Very soluble. Ex. No.137b j j Fifth Stage Resin to EtO Molal Ratio 1:20" 2. 05 3. 65 6. 2. 05 3. 13. 35 k; Very soluble. Ex. No. 138b Date, Sept. 2321,1948

[Resin made on pilot size batch, approximate1y25 pounds, corresponding to 89a 0f Patent 2,499,370 but this batch designated as 13942.]

Bhenol for resin: Menthyl Aldehyde I01: resin: Eu rfural Mix Which is Mix Which Re- Starting Mix fig figg Removed for mains as Next Sample Starter Max. Max. Time 1 ljressupe gempsroahrs Solubility s.sq.m. ure Lbs. Lbs. Lbs Lbs. Lbs. .Lbs. Lbs. Lbs Lbs- Lbs. 'Lbs Sol- Res- Eto Sol- Res-- Res- Sol- Res- Eto vent in vent in vent in vent. "in

First Stage Resin to EtO i Molal Ratio 1:1--. 10.25 17.75 10.25 17.75 2.5; 2.65 4.60 0.65 16113.15 1.85 90 150 36 Not soluble Ex. No. 139b i Second Stage Resin to. Et0 Molal Ratio 1:5.-- 7.6 13.15 1.85 7.6 13.15 9.35 5.2, 9.00 6.40 2.4 4.15 2.95 80 177 $6 Somewhat Ex. No. 140!) soluble.

Third Stage Resin to EtO. MolalRatio1:10 4.22 6. 98 4.22 6.98 10.0 I 90 16 }4 Soluble. Ex. No. 141!) Founh Stage Resin to EtO MolalRatio 1:15-- 3. 76 6. 3.76 6.24 13.25 100. 171 3a Verysoluble. Ex.No.142b

Fifth Stage Resin to E-.. l Mo1alRatio1:20 2.4 4.15 2.95 2.4 4.15 11.70 90 150 k; Verysoluble. Ex. No. 143114....

2,542,013 29 4o 6 4 Phenol f? i-esin: Para-octyl Aldehyde for resin): Furfural Date, October 7-8, 1948 [Resin made on pilot plant size batch. approximately pounds, corresponding (1042a of Patent 2.499.370 with 206 parts by weight of commerciai 1 p'ara-octylp'lienol replacing 164 parts by weight of para-tertiary amylphenol but this batch designated as 144a.]

Mix Which is ,Mix Which Re- Starting Mix ai 23 3 of Removed for mains as Next ea Sample Starter Max. Max. Time l1Rressure "tlemp eaa- Solubility Lbs Lbs Lbs. Lbs Lbs. Lbs. Lbs. Lbs. r

Lbs Lbs. Lbs. Lbs. Sol- Res- Sol- 'Res- 801- Res- Sol- Resvent in Eto vent in Eto vent in Eto vent in Eto First Stage Resin to EtO Molal Ratio 1:1 12.1 18. 6 12.1 18. 6 3.0 5.38 8. 28 1. 34 6. 72 10.32 1. 66 80 150 M2 Insoluble. Ex. No. 144b.

Second Stage Slight tend- Resin to EtO V ency to- Molal Ratio 1:5 9. 25 14. 25 9. 25 14. 25 11. 0 3. 73 5. 73 4. 44 5. 52 8. 52 6. 56 100 177 942 Ward bo- Ex. No. 145b coming soluble. Third Stage Resin to mom. Molal Ratio 1:10. 6 72 10. 32 1. 66 6. 72 10. 32 14. 91 4. 97 7. 62 11. 01 1. 75 2. 3. 90 85 182 $4 Fairly so1u- Ex. No. 14Gb. ble.

Fourth Stage Resin to EtO Molal Ratio 1:15. 5. 52 8. 52 6. 56 5. 52 8. 52 19. 81 100 176 M; Readily sol- Ex. No. 147b uble.

Fifth Stage Resin to EtO..-. Mola] Ratio 1:20. 1. 2. 70 3.90 1.75 2. 70 8.4 160 $4 Quite solu- Ex. No. 1480.-..-- blc.

Phenol for resin: Pard-phen'yl Aldehyde for resin: Furfural Date, October 11-13, 1948 [Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 42a of Patent 2.499.370 with 170 parts by weight of commercial paraphenylphenol replacing 164 parts by weight of para-tertiary amylphenol but this batch designated as 149a.1

. Mix Which Is Mix Which Re- Starting Mix fijg figg of Removed for mains as Next Sample Starter Max. Max. Time Pressure Temp era- Solubility i b s. abs. Lbs l b s. I bs. Lbs l b s. gbs. Lbs lbls. abs. Lbs

o eso eso es- 0 esvent in Eto vent in Eto vent in Eto vent in Em First Stage Resin to 13120.... Molal Ratio 1:1 13 9 16.7 13.9 16.7 3.0 3.50 4.25 0.80 -"10.35 12.45 2.20 M4 Insoluble. Ex. No. 149b Second Stage Resin to EtO i? i Molal Ratio 1:5 10.35 12.45 2.20 10.35 12.45 12.20 5.15 6.19 6.06 5.20 6. 26 6.14 80 183 $5 e g Ex No.150b

' bility.

Third Stage Resin to EtO. Molal Ratio 1:10- 8.90 10.7 8.90 10.70 19.0 5.30 6.38 11.32 3.60 4.32 7.68 90 193 iz'Fairly solu- Ex. No.151b bla.

Fourth Stage Resin to EtO.- Molal Ratio 1:15. 5.20 6.26 6.14 5. 20 6.26 16. 64 100 171 $6 Readily s01- Ex. No. 1521)"..- uble.

Fifth Stage Resin to EtO-- Sample somewhat rubbery and gelatlloleil Ragieoblfio- 3 60 4.32 7.68 3.60 4.32 15.68 inous but fairly soluble 230 2 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING A MIXED HYDROPHILE ESTER IN WHICH THE ACYL RADICALS INCLUDE AN ACYL RADICAL OF A DETERGENT-FORMING MONOCARBOXY ACID HAVING AT LEAST 8 AND NOT OVER 32 CARBON ATOMS IN CONJUNCTION WITH THE ACYL RADICAL OF AN ALPHA-HALOGEN MONOCARBOXY ACID HAVING NOT OVER 6 CARBON ATOMS, AND IN WHICH THE ALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILE POLYHYDRIC SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE, AND (B) AN OXYALKYLATION - SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENTSOLUBLE, WATER-INSOLUBLE PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 